Basic azo dyestuffs containing an n-acyl-amino-n&#39;-pyridinium lower alkyl-eneaminophenyl group

ABSTRACT

BASIC AZO DEYSTUFFS, WHICH ARE FREE FROM ACIDIC GROUPS IMPARTING SOLUBILITY IN WATER OF THE FORMULA   1-(D-N=N-),3-(R-O-),4-(&gt;N(+)(-X)-Y-N(-R&#39;&#39;)-),6-A-BENZENE   IN WHICH D REPRESENTS THE RESIDUE OF A DIAZO COMPONENT, A AN ACYLAMINO GROUP, Y A LINAR OR BRANCHED ALIPHATIC CARBON CHAIN, R&#39;&#39; REPRESENTS HYDROGEN OR AN ALKYL, ARALKYL OR CYCLOALKYL RESIDUE, R AN ALKYL, ARALKYL, CYCLOALKYL OR ARYL RESIDUE AND X AN ANION. THE DYESTUFFS ARE SUITABLE FOR USE IN DYEING AND PRINTING; ARE SUITABLE FOR THE BULK COLORATION OF POLYACRYLONITRILE POLYMERS AND ARE FAST TO LIGHT AND WASHINGS.

United States Patent 3,640,993 Patented Feb. 8, 1972 US. Cl. 260146 R 11 Claims ABSTRACT OF THE DISCLOSURE Basic azo deystuifs, which are free from acidic groups imparting solubility in water of the formula in which D represents the residue of a diazo component, A an acylamino group, Y a linear or branched aliphatic carbon chain, R represents hydrogen or an alkyl, aralkyl or cycloalkyl residue, R an alkyl, aralkyl, cycloalkyl or aryl residue and X an anion. The dyestuffs are suitable for use in dyeing and printing; are suitable for the bulk coloration of polyacrylonitrile polymers and are fast to light and washings.

The present invention provides new azo dyestuifs which are free from acidic groups imparting solubility in water, especially sulphonic and carboxylic acid groups, of the formula in which D represents the residue of a diazo component, A an acylamino group, Y a linear or branched aliphatic carbon chain containing preferably no more than four carbon atoms, R represents hydrogen or an alkyl, aralkyl or cycloalkyl residue, R an alkyl, aralkyl, cycloalkyl or aryl residue and X represents an anion.

According to the present invention the new dyestuffs may be manufactured by amidation or condensation or coupling. The manufacture by amidation or condensation is carried out by treating a reactive dyestuif derivative with a cyclic amine that contains a reactive atom or a reactive group. Thus, for example, a compound of the formula (2) D-IhmQJI-Y-Z in which D, A, R, R and Y halve the above meanings and Z represents a reactive atom or a reactive group, for example a halogen atom or an ester grouping, may be reacted with an amine of the formula in which Y and X have the above meanings and Z represents a reactive atom or a reactive group, for example a halogen atom or a sulphato group, may be reacted with a compound of the formula n-rarQnuw in which D, A, R and R have the above meanings.

The manufacture by coupling may be carried out by coupling a diazo compound with a coupling component of the formula in which A, R, R, Y and X have the above meanings.

Azo dyestutfs that may be mentioned are those obtained by coupling a diazotized amine, preferably of the aromatic or heterocyclic series, with a coupling component derived from an etherified 2-amino-4-acylaminophenol. A list of suitable diazo and coupling components is given below in connection with the explanation of the manufacture by coupling.

These dyestuffs are reacted according to process (a) of the present invention with an amine of the Formula 3 or 4. Suitable amines of the Formula 3 are, for example: Pyridine, picoline, lutidine, quinoline and pyrimidine. As an amine of the Formula 4 N-fl-chlorethylpyridinium chloride may be mentioned.

The reaction of the dyestuff containing, for example, a halogenor sulphato-alkyl group, with the amine is carried out in a neutral solvent, for example in chlorobenzene, an alcohol, an aqueous alcohol mixture or in dimethylformamide, or if desired without a solvent, advantageously at an elevated temperature in an excess of the amine and, if desired, in the presence of a catalyst, for example sodium iodide.

According to process (b) of the invention an amine may also be reacted with a dyestutf intermediate instead of with the dyestuif, and subsequent coupling of the reaction products thus obtained gives rise to the final product.

As examples of diazo components aromatic compounds may be mentioned in the first place, for example those of the naphthalene or especially the benzene series. These compounds may correspond, for example, to the formula xii-Qatar in which X represents a hydrogen or halogen atom, a cyano, carbalkoxy, alkanoyl, alkylsulphonyl, carbonamide, sulphonarnide, phenylazo or nitro group, Y represents a hydrogen or halogen atom, a nitro, alkyl, alkoxy, trifluoromethyl, carbalkoxy or cyano group, Z a hydrogen or halogen atom, a nitro or alkylsulphonyl group, and at least one of the residues X or Y is a halogen atom, a nitro, carbalkoxy, cyano, alkylsulphonyl or phenylazo group.

As examples the following aminobenzenes may be mentioned: l-amino-Z-chlorobenzene, 1-amino-4-chlorobenzene, l-amino-4-bromobenzene, l-amino-Z-nitrobenzene, 1-amino-3-nitrobenzene, 1-amin0-4-nitrobenzene, l-amino-4-cyanobenzene, l-amino-Z-methoxybenzene, l-amino-4-methoxybenzene, 1-amino-2,5-dicyanobenzene, l-amino-4-carbalkoxybenzene, 1-amino-2,4-dibromobenzene, 1-amino-2,4-dichlorobenzene, 1-amino-2,S-dichlorobenzene, l-amino-2-methyl-4-chlorobenzene, 1-amino-2-nitro-4trifiuoromethylbenzene, 1-amino-2-trifluoromethyl-4-chlorobenzene, l-amino-3-trifluoromethyl-2-chlorobenzene,

2-amino-5mitrotrifluoromethylbenzene, 1-amino-2-cyano-4-chlorobenzene, 1-amino-2-cyano-4-nitrobenzene, 1-amino-2-nitro-4-methoxybenzene,

2-aminobenzoic acid methyl ester,

4-aminobenzoic acid-fi-methoxyethyl ester, 2-amino-5-chlorobenzoic acid methyl ester, Z-amino-S-nitrobenzoic acid methyl ester, 4-aminobenzoic acid-fi-dimethylaminoethyl ester, 4-aminobenzoic acid-y-dimethylaminopropylamide, 4-amino-3-nitrobenzoic acid-,B-diethyl-aminoethyl ester, 4-amino-3-nitrobenzoic acid-'y-dimethylaminopropylamide, v sulphanilic acid-fl-N-trimethylaminoethylamide, l-amino-2-chloro-4-cyanobenzene, l-amino-2-chloro-4-nitrobenzene,= l-amino-4-chloro-2-nitrobenzene, V 1-amino-2-chloro-4-carbethoxybenzene, l-amino-2-methylsulphonylbenzene, l-amino-4 methylsulphonylbenzene, H 1-amino-2-methylsulphonyl-4-nitrobenzene, I l-amino-6-methylsulphonyl-2,4dinitrobenzene, 1-amino-2-chloro-4-methylsulphonylbenzene, 1-amino-2,4-dinitrobenzene, r 1-amino-2,4-dicyanobenzene, 1-amino-2,6-dichloro-4-cyanobenzene, 1-amino-2,6-dichloro-4-nitrobenzene, 1-amino-2,4-dicyano-6-chlorobenzene, 1-amino-2,4-dinitro-fi-chlorobenzene, 1-amino-2-cyano-4-nitro-fi-chlorobenzene, l-amino-Z-cyano-4-nitro-6-bromobenzene, 1-amino-2,4-dinitro-6-bromobenzene, l-amino2,4-dinitro-6-cyanobenzene, 3-amino-benzenesulphonic acid amide, 4-aminobenzenesulphonic acid monoethylamide, 4-amino-3-chlorobenzenesulphonic acid diethylamide, 4-amino 3-chlorobenzenesulphonic acid monoethylamide, 4-aminobenzenesulphonic acid ethyl ester, 4-aminoazobenzene, 4-amino-2'-chloro-azobenzene, 4-amino-2',4-dichloro-azobenzene, 4-amino-3'-chloro-azobenzene, 4-amino-2-nitro-azobenzene, 4-amino-3-nitro-azobenzene, 4-amino-3'-nitro-azobenzene, 4-amino-2-methyl-azobenzene, 4-amino-4'-methoxy-azobenzene, 4-amino-3-nitro-2'-chloroazobenzene, 4-amino-3-nitr0-4'-chloroazobenzene, I 4-amino-3-nitro-2',4'-dichloro-azobenzene and 4-amino-3-nitro-4'-methoxy-azobenzene.

The diazo component used may also be any desired diazotizable heterocyclic amine that is free from acidic substituents imparting solubility in water, more especially amines that contain a S-membered heterocycle'contain ing 2 or 3 hetero atoms, especially one nitrogen and one or two sulphur, oxygen or nitrogen atoms as hetero atoms;

5 2-amino-1,3,4-thiadiazole, 2-amino-1,3,5-thiadiazole and 2-amino-4-phenyl-l,3,5-thiadiazole.

As coupling components the following examples may be mentioned: in these formulae Q represents a cyclic amino group of the formula bound through the nitrogen atom or, when this group is only subsequently introduced by condensation according to manufacturing process (a), a reactive atom or a reactive group, for example, a halogen atom, a sulphate group or an arylor alkyl-sulphonyloxy group.

oca S 5 cit NHC H Q C l'l4 Q 7 rncoctr mucosa (M3 c H OCH; c a CH 2 5 2 4 K c 1r Q H Q nrzcocir M10061;

OCH

3 oc iz 2 4 Q c a Q :ntcocit nicoocn ocn oca 5 3 ea c H 021 3 2 4 H c H Q "2 4 Q 2 4 IHCOC2H5 mtcoca 0on can 6 H ON 0 x1 Q 0 x Q mtcomt NHCONHCZHS oc u, 2

c n coocn r c a c n Q .7 0 11,, Q moons lracocn OCH NHCOCH N SO Instead of a single diazo component a mixture of two or more of the diazo components according to the invention and instead of a single coupling component a mixture of two or more of the coupling components according to the invention may be used.

The above-mentioned diazo components may be diazotized by known methods, for example with a mineral acid, especially hydrochloric acid, and sodium nitrite, or, for example, with a solution of nitrosylsulphuric acid in concentrated sulphuric acid.

The coupling may also be carried out in known manner, for example in a neutral to acid medium, if desired in the presence of sodium acetate or a similar buffer capable of influencing the rate of coupling or of a catalyst, for example pyridine or a salt thereof.

Should purification of the dyestufi salts be at all necessary, it is advantageously carried out by dissolving them in Water; any unreacted starting dyestutf forms an insoluble residue which can be filtered. The dyestutf can be precipitated again from the aqueous solution by addition of a water-soluble salt, for example sodium chloride.

The quaternated dyestuffs obtained by the present invention preferably contain as anion the residue of a strong acid, for example sulphuric acid, or a semi-ester thereof, or of an arylsnlphonic acid or a hologen ion. The said anions, which according to this invention are introduced into the dyestutf molecule, may if desired, be replaced by anions of other inorganic acids, for example phosphoric or sulphuric acid, or of organic acids, for example for formic, lactic or tartaric acid. In certain cases the free bases may be used. The dyestuff salts may, if desired, be used in form of double salts, for example with halides of the elements of Group 2 of the Periodic Table, especially with zinc chloride or cadmium chloride.

The new dyestufis or dyestulf salts containing a quaternated amino group are suitable for dyeing or printing a wide variety of fully synthetic fibres, for example polyvinylchloride, polyamide or polyurethane fibres, also fibres of polyesters of aromatic dicarboxylic acids, for example polyethylene terephthalate fibres, and especially materials consisting of polyacrylonitrile fibres or polyvinylidene cyanide fibres (Darvan-a registered Trademark). The term polyacrylonitrile fibres is to be understood to include mainly polymers containing more than 80%, for example 80 to 95% of acrylonitrile;; in addition they may contain to of vinyl acetate, vinyl pyridine, vinyl chloride, vinylidene chloride, acrylic acid, acrylic esters, methacrylic acid and methacrylic esters. These products are marketed, for example, under the following registered trade names: Acrilan 1656" and Acrilan 41 (The Chemstrand Corporation, Decatur, Ala., U.S.A.), Creslan (American Cyanamide Company), Orlon 44 (Du Pont), Crylor HH (Soc. Rhodiacta SA, France), Leacril N (Applicazioni Chimice S.A., Italy), Dynel (Union Carbide Chem. Corp.), Exlan (Japan. Exlan Industry Co., Japan), Vonnel (Mitsubishi, Japan), Verel (Tennessee Eastman, U.S.A.), Zefran (Dow Chemical, U.S.A.), Wolcrylon (Filmfabrik Agfa, Wolfen), Ssaniw (U.S.S.R.) and Orlon 42, Dralon, Courtelle and the like.

On these fibres, which may also be dyed in admixture with one another, the new dyestuffs produce deep and level shades having good light fastness and good general fastness properties, especially good fastness to washing, perspiration, sublimation, creasing, decatizing, ironing, rubbing, carbonizing, Water, sea water, dry-cleaning, overcleaning, over-dyeing and solvents. The new dyestuffs of this invention also display, inter alia, good stability within a considerable pH range, good affinity, for example in aqueous solutions of various pH values and good fastness to caustic kier boiling. Moreover, the new dyestuffs generally reserve well on wool and other natural polyamide fibres.

The quaternated, water-soluble dyestuffs are in general a little sensitive to electrolytes and some of them are readily soluble in water or in polar solvents. Dyeing with the quaternated, water-soluble dyestuffs is generally performed in aqueous neutral or acid media, at the boil under atmospheric pressure or in a closed vessel at an elevated temperature and elevated pressure. They are not affected by commercial levelling agents, but these agents are not necessary either.

The new dyestuffs are especially suitable for three colour dyeing. Furthermore, by virtue of their stability to hydrolysis they may be advantageously used for hightemperature dyeing and for dyeing in the presence of wool. They may also be used for printing fibrous materials, for example with a printing paste that contains the dyestuif together with the assistants generally used in printing. They are also suitable for the bulk colouration of acrylonitrile polymers as well as other plastic masses, if desired in solution, shades fast to light and washing, and for colouring oil paints and lacquers. They may also be used for dyeing cotton, especially mordanted cotton, cellulose, regenerated cellulose and paper.

According to the present process the new dyestuffs may also be used for printing, for example with a printing paste that contains the finely dispersed or dissolved dyestutf, together with the assistants generally used in printing, for example wetting or thickening agents, if desired in the presence of an organic and/or inorganic acid.

The dyeings and prints obtained by the above processes have good tinctorial strength and excellent fastness properties, especially fastness to light, sublimation, decatizing, washing, and chlorine water. Another advantage is that the dyestuffs to be used according to this invention resist wool and other natural polyamide fibers well.

Unless otherwise indicated, parts and percentages in the following examples are by weight.

EXAMPLE 1 4.35 parts of 2-chloro-4,6-dinitroaniline are added at room temperature to parts by volume of N nitrosylsulphuric acid. The reaction mixture is stirred for 1 hour at 20 to 25 C., then stirred into 100 parts of ice and the excess nitrous acid decomposed with sulphamic acid. The resulting diazo solution is immediately added to a solution of 9.42 parts of N,2-(N'-[2'-methoxy-5'-acetylarhino- 8 phenyl]-N-methyl)-aminoethyl-pyridinium toluene sulphonate in parts of water and 100 parts of ice. The whole is stirred for 1 hour, the dyestuif is filtered, dissolved again in 500 parts of water and 5 parts of crystalline sodium acetate and salted out with 10 parts of sodiumbromide. After drying, a black dyestuff powder is obtained which dyes polyacrylonitrile fibres from an aqueous bath navy shades that are very fast to light.

Manufacturing the coupling component pyridine are refluxed for 4 hours at a bath temperature of 150 C. The pyridinium salt thus formed can be ob{ tained in crystalline form by diluting the cooled melt with' ethyl acetate. If desired, the clear solution obtained by diluting the melt with water may be used as it is for coupling.

. EXAMPLE 2 20 parts of 2-chloro-4-nitro-6-cyanoaniline are added at 0 to 5 C. to a mixture of parts by volume of N nitrosylsulphuric acid and 100 parts by volume of a 6: 1- mixture of glacial acetic acid and propionic acid. Another 100 parts of the glacial acetic acid+propionic acid mixture are then added and the whole is stirred for 2 hours in an ice bath, 10 parts of urea are then added and the yellowish diazo solution is added to a well stirred mixture of 36.4 parts of a coupling component of the formula in 1000 parts of water and 500 parts of ice. The dyestuif, which precipitates in an acid solution, is suction filtered, suspended in 2000 parts of water and dissolved by adding crystalline sodium acettae until the solution reacts neutral to Congo red. The dyestuff is salted out with-1 0d parts of sodium chloride, filtered and dried; it corresponds to the formula v and dyes polyacrylonitrile fibres fast blue tints.

Further dyestuffs of the general formula are listed in the following table; they are accessible by coupling as described in Examples 1 and 2.

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............................ 5 8 amov mooomz zo mo mo 8 mm n ..8..... :58 moo 0M2 m 50 8 S 6Q 32E 8 25m .L QMOYI EU 0 o OHMZI. EDI GENO! 26% 3 08am :S m w o z o z 5 8 6 L Qmov "mo 0 omz mu mo z o 2 2 am G W 4 \M M Q Dyeing instruction C (high-temperature dyeing process) 2 parts of dyestuff are dissolved in 3000 parts of water with addition of 1 part of crystalline sodium acetate, parts of calcined Glaubers salt and sutficient acetic acid to attain a pH value from 4.5 to 5. 100 parts of polyacrylonitrile filament yarn are immersed at 80 C. in this bath, the temperature is raised during 45 minutes to a maximum of 120 C. and dyeing is carried out for 30 minutes at 120 C. The whole is then slowly cooled and the yarn rinsed.

Dyeing instruction D (printing) NH-Acyl 2 wherein D is a member of the group consisting of thiazol- 2-yl-, 5-nitrothiazol-2-yl-, 5-cyanothiazol-2-yl-, 4-methyl- 5-nitrothiazol-2-yl-, 4-methylthiazol-2-yl-, 4-phenylthiazol- 2 yl 4-(4'-chloro-)phenylthiazol-2-yl-, 4-(4'-uitro-) phenylthiazol 2 yl-, benzthiaz0l-2-yl-, 6-methylbenzthiazol-2-yl-, 6-methoxybenzthiazol-2-yl-, 6-chlorobenzthiazol-2-yl-, G-nitrdbenzthiazol-Z-yh, 6-cyanobenzthiazol- 2-yl-, 6-canboethoxybenzthiazol-2-yl-, 6-methylsulfonylbenzthiazol-2-yl-, triazol-2-yl-, 1,3,4-thiadiazol-2-yl-, 1,3,5- thiadiazol-Z-yland 4-phenyl-l,3,5-thiadiazol-2-yl-, R is phenyl, benzyl or C -C -alkyl, R is hydrogen, benzyl or C alkyl or said alkyl substituted by cyano or C alkoxy, Y is (CH or -(CH acyl is C -C alkanoyl, benzoyl, C -C -alkoxycarbonyl, phenylsulfonyl, methylsulfonyl, aminocarbonyl or aminocarbonyl N-substituted by phenyl or C -C -alkyl, and wherein the pyridinium radical is unsubstituted or substituted by methyl, and X is an anion.

2. A basic azo-dyestuif as claimed in claim 1, wherein acyl is acetyl.

3. A lbasic azo-dyestutf as claimed in claim 2, wherein X and Y is nitro or cyano and Z is chlorine or bromine.

4. Basic azo dyestufr as claimed in claim 1, wherein R represents ethyl or methyl.

5. Basic azo dyestufi as claimed in claim 1, where X'- represents Cl, Br, I, =SO -SO -alky1, SO aryl or SO O-a1kyl.

6. The :basic azo dyestutf of the formula 7. The basic azo dyestufi of the formula 3 O NQIMQN OCH uncooc n 5 8. The basic azo dyestuff of the formula 9. The basic azo dyestuff of the formula 11. The basic azo dyestulf of the formula OCH nncocu References Cited UNITED STATES PATENTS FLOYD D. HIG'EL, Primary Examiner US. Cl. X.R. 

